JPH051285B2 - - Google Patents

Abstract

The present invention relates to copolymers which can be used as adhesion mediating agents (adhesivers) between polymers and inorganic-oxide material. They are characterized by a reactive alkoxysilyl group and an acrylic or methacrylic acid moiety. Each of these two groups is linked to a fundamental constituent having two chain carbon atoms, this fundamental constituent being constructed on a compound having an ethylenically unsaturated group as monomer. The ratio of the alkoxysilyl groups to the acrylic or methacrylic acid esters in the new copolymers can be established as desired, for example by copolymerizing the copolymers with other compounds having ethylenically unsaturated groups, which do not have the above-named moieties. The present invention also relates to a method of preparing these new copolymers as well as intermediates which occur in the practice of this method, as formerly unknown products.

Description

[Detailed description of the invention]

The object of the present invention is produced by radical polymerization,
With reduced viscosity from 0.02 to 2.0, general formula: [In the formula, Hal is a halogen atom which may be optionally substituted with an acrylic acid or methacrylic acid group, R is a hydrogen atom or a methyl group, and R ¹ is 1 to
Alkyl group with 16 C-atoms, R ² is 1-4
alkyl radicals having a C-atom of General formula ~

【formula】

【formula】

【formula】

[Formula] (In the formula, R represents the above, R ³ is a hydrogen atom or an alkyl group having 1 to 18 C-atoms, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 C-atoms. B is one of the non-functional structural basic units of the general formula ~

【formula】

【formula】

[Formula] (wherein n may be 3 to 5, the ring between the two C-atoms may be interrupted by oxygen, and R ⁵
is an alkyl group having 1 to 3 C-atoms and R
is a hydrogen atom or a methyl group) and a and b each represent 0 to 99% by weight and the sum of a and b = 0 to 99% ] is a new copolymer that is effective as an adhesive. Furthermore, the copolymers resulting from the production of these new polymeric adhesives, as well as the process of making the new polymeric adhesives from these new copolymers resulting as intermediate products, are also within the scope of the present invention. Copolymers in which one of the structural basic units with two chain carbon atoms has an alkoxysilyl group directly bonded to the structural basic unit are already known from DE 26 24 888 A1. However, another ethylenically unsaturated structural unit with two chain carbon atoms is only connected to an acid group or an anhydride group or an ester group. These compounds are not directly suitable as adhesives between polymers and inorganic oxide materials. These compounds exhibit special adhesive action only when used in mixtures with organofunctional silanes. Furthermore, it is known, for example from West German Pat. It is. However, the use of these compounds as adhesives is limited by the presence of relatively high concentrations of methacrylate components in the molecules, so that these compounds can be used in uniform distribution to form polymers and fillers. It is often used in too large a concentration in the mixture of agents to be bound. In many cases, lower concentrations of acrylate groups compared to alkoxysilyl groups also promote or enhance adhesion to the polymer as well. Therefore, a) the acrylate and methacrylate groups contain alkoxysilyl groups and the concentration of the acrylate or methacrylate groups and the alkoxysilyl group can be varied within a wide range, either absolutely or relatively, and b West Germany The object was to provide a new class of adhesives having at least as good adhesion promoter action as the silanes of Patent No. 1270716. Another challenge was finding a way to make such an adhesive. By the way, in solving this problem, 0.02 to 2.0
With a reduced viscosity of, the general formula: [In the formula, Hal is a halogen atom which may be optionally substituted with an acrylic acid or methacrylic acid group, R is a hydrogen atom or a methyl group, and R ¹ is 1 to
Alkyl group with 16 C-atoms, R ² is 1-4
alkyl radicals having a C-atom of General formula ~

【formula】

【formula】

【formula】

[Formula] (In the formula, R represents the above, R ³ is a hydrogen atom or an alkyl group having 1 to 18 C-atoms, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 C-atoms. B is one of the non-functional structural basic units of the general formula ~

【formula】

【formula】

[Formula] (wherein n may be 3 to 5, the ring between the two C-atoms may be interrupted by oxygen, and R ⁵
is an alkyl group having 1 to 3 C-atoms and R
is a hydrogen atom or a methyl group) and a and b each represent 0 to 99% by weight and the sum of a and b = 0 to 99% ] copolymers were discovered. Furthermore, a process has been found for producing polymers in which one of the basic structural units contains an acrylic acid or methacrylic acid group. This method comprises preparing a copolymer according to the invention having a plurality of structural basic units each having two chain carbon atoms, one structural basic unit being bonded to an α-halogencarboxylic acid group, using acrylic acid or methacrylic acid. It is characterized by reaction with an alkali metal salt or alkaline earth metal salt of an acid. The copolymers according to the invention exhibit excellent adhesion between inorganic oxide materials and polymers. This effect is due to the fact that only a minimum of 0.5% or a maximum of 0.5% by weight of structural basic units with acrylic acid or methacrylic acid groups
It also occurs when present in 99.5% by weight polymer.
All intermediate values in between are possible. According to the invention, the novel copolymers can therefore also contain further structural basic units known per se, which contain neither acrylic or methacrylic acid groups nor alkoxysilyl groups, and which have two chain carbon atoms. It is possible. Such additional structural units may be present in the polymer in such amounts that the proportion of structural units containing alkoxysilyl groups and (meth)acrylate groups is at least 0.5% by weight each. The structural basic unit having an α-halogencarboxylic acid group is derived from an α-chloro- or α-bromo fatty acid vinyl ester. The fatty acid groups are preferably those having 2 or 3 carbon atoms, but higher fatty acids having up to 18 carbon atoms can also be used. Preferred monomers are α-chloro-
or vinyl bromoacetate ester. Structural basic units with one alkoxysilyl group are, on the one hand, described in West German Patent Application No.
It is the same as that contained in the compound of No. 2624888. Additionally, these structural basic units may optionally contain alkoxysilyl groups.

It may also be bonded via a group [formula] to one of the C atoms of the structural basic unit, as for example in γ-methacryloxypropyltrimethoxysilane. Examples of monomers from which these basic structural units are formed are vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriethoxysilane.
Vinyltrialkoxysilanes whose alkoxy groups preferably have up to 4 carbon atoms, such as (2-methoxyethoxy)-silane and γ-methacryloxypropyltrimethoxysilane. Further structural basic units which contain neither acrylate or methacrylate groups nor alkoxysilyl groups optionally contained in the copolymers according to the invention are ethylenically unsaturated monomers containing alkoxysilyl groups and α - monomers copolymerizable with ethylenically unsaturated monomers containing halogen carboxylic acid groups, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, diethyl maleate, diethyl fumarate, Derived from monomers such as maleic anhydride, ethyl acrylate and methyl methacrylate. These groups, also referred to herein as non-functional structural basic units, can be represented by the following formula:

【formula】

【formula】

【formula】

[Formula] [In the formula, R represents a hydrogen atom or a methyl group,
R ³ represents a hydrogen atom or an alkyl group having 1 to 18 C atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 C atoms]. Suitable corresponding non-functional vinyl monomers as starting materials for the corresponding structural units in the copolymers are well known to those skilled in the art. Furthermore, the copolymers according to the invention, together with or instead of selectively polymerized non-functional monomers, impart water-solubility or water-emulsifiable properties to the polymer up to 99% by weight.

【formula】

【formula】

[Formula] (wherein n may be 3 to 5, the ring between the two C-atoms may be interrupted by oxygen, and R ⁵
is an alkyl group having 1 to 3 C-atoms and R
is a hydrogen atom or a methyl group), such as N-vinylpyrrolidone, methyl vinyl ether, N-vinylmorpholinone-3, N-vinyl-1, 3-Oxazidinone - such another functional monomer or functional group that can later form salts with acids or bases, but does not react with alkoxysilyl groups, or halogen functional groups or acrylate or methacrylate functional groups. ethylenically unsaturated compounds such as maleic anhydride, itaconic anhydride, 2-diethylaminoethyl acrylate or -methacrylate. Ethylenically unsaturated monomers, which form the basis of each basic structural unit, can be easily copolymerized by known radical polymerization methods. The initiators used in the polymerization are, for example, compounds known for this purpose, such as organic peroxides or azoinbutyric acid dinitrile. Examples include: benzoyl peroxide, diacetyl peroxide,
Methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumol hydroperoxide, tert.-
Butyl hydroperoxide, di-tert.-butyl peroxide, dicumyl peroxide, 1,3-di-tert.-butylperoxyisopropylbenzole, tert.-butylberacetate, tert.-butyl-peroctate, tert.-butylperoxide pivalate, tert.-butyl isononanate. The catalyst is added in an amount of 0.2 to 3% by weight for the polymerization of ethylenically unsaturated monomers, which amount is usually sufficient to obtain a suitable reaction rate and high monomer conversion. Bulk polymerization to obtain copolymers according to the invention, in which the carboxylic acid groups bonded to the structural basic units are halogen-substituted, ie can be carried out without the additional use of diluents or solvents. However, the polymerization is preferably configured as a solution polymerization. As the solvent, it is possible to use a solvent that inhibits polymerization in some way or does not react with the alkoxysilyl group or the halogen carboxylic acid group of the vinyl monomer in some way. Suitable solvents are, for example, fatty acid esters, such as ethyl acetate, ketones, such as acetone or methyl ethyl ketone, or aromatic hydrocarbons, such as benzol or toluol. The weight ratio of vinyl monomer and solvent is 4:1 ~
It is possible to reach a ratio of 1:4. The aforementioned copolymerizations are generally carried out such that all the monomers are placed together in a reaction vessel and reacted randomly depending on their relative concentrations and relative reactivities to form a statistical polymer. However, it is also possible to meter in one or more ethylenically unsaturated monomers during the course of the polymerization in order to increase or reduce the nonuniformity of the polymer. Furthermore, the polymerization is carried out as a graft copolymerization, optionally up to three ethylenically unsaturated monomers corresponding to the structural basic units being added to the remaining structure contained in the copolymer according to the invention. It is also possible to graft preformed polymers containing the basic units in a manner known per se. This type of reaction is generally known in the field of radical polymerization. The production of polymers whose structural basic units are bonded to functional acrylic or methacrylic groups, which are effective as adhesives, involves the production of copolymers in which one of the structural basic units is bonded to a halogen carboxylic acid group. Alternatively, it is carried out by reacting with an alkali metal salt or alkaline earth metal salt of methacrylic acid. The alkali metal salt of acrylic acid or methacrylic acid contains one acrylate or methacrylate per gram atom of chlorine in the starting copolymer.
It is used in such an amount that ~1.5 moles are available.
Advantageously, this ratio is 1:1.1. A preferred embodiment of the reaction uses a solution of the starting copolymers mentioned above, such as occurs, for example, during solution polymerization to produce copolymers according to the invention having basic units containing halogencarboxylic acid groups. consists of doing. However, the solvent used in that case can also be partially or completely replaced by a solvent suitable for the reaction during the polymerization. Due to the particular reactivity of the alkoxysilyl groups in the corresponding basic units, the selection of suitable solvents is strongly restricted. In many cases, the solubility of alkali metal salts of alkali acrylic and -methacrylic acids in the solvents that can be used is only low. This has an adverse effect on the reaction rate of the reaction, which is therefore generally very slow. In another embodiment of the invention, this disadvantage is overcome by carrying out the reaction with the acrylate in the presence of a phase change catalyst. Suitable phase change catalysts are, for example, crown ethers or special quaternary ammonium or phosphonium salts, such as in particular tetrabutylammonium chloride, tetraphenylphosphonium bromide, trimethylbenzylammonium bromide, methyltricaprylylammonium chloride. Crown ethers that can be used include 12-crown-4, 24-crown-8, and dibenzo 18-crown ether-6.
can be given. Other crown ethers and ammonium or phosphonium salts that can be used are known from the literature to those skilled in the art. Due to the process, the polymer solutions used in the reaction with alkali metal salts of alkali acrylic and methacrylic acids can still contain residual initiators with which they were used during their preparation.
The presence of this initiator is difficult insofar as, upon reaction with alkali acrylates, the acrylate- or methacrylate-containing polymer structural units are excited thereby and undergo intramolecular crosslinking reactions with the formation of three-dimensional network structures. may occur. However, this intramolecular crosslinking should be prevented as much as possible during the preparation of these polymers. Therefore, when producing the adhesive according to the invention,
It is advantageous to render the residual initiator contained in the starting polymer inert. This means, according to the invention, that before the reaction of these polymer solutions with alkali metal or alkaline earth metal salts of acrylic acid and methacrylic acid, the decomposition temperature of the radical former is maintained until the initiator is completely destroyed. This is done by heating to a temperature higher than that. The initiator can also be made inert by the addition of stabilizers, such as, for example, di-tert.-butylcresol, hydroquinone monomethyl ether, phenol, pyrogallol, hydroquinone or phenothiazine, which act as polymerization inhibitors. Other suitable stabilizers are known to those skilled in the art. If used in an amount of about 0.01 to 3% by weight based on the polymer,
These stabilizers prevent intramolecular cross-linking of the polymeric adhesive during manufacture, processing, and storage. The reaction with acrylate or methacrylate must not be complete. It is sufficient that the reaction proceeds to such an extent that the resulting polymer contains at least 0.5% by weight of structural basic units to which methacrylic groups are bonded. The copolymer obtained by this reaction acts as an adhesive between the polymer and the filler, pigment or dye. This polymer is produced by free radical reaction with 3
Any polymer that can be modified into a dimensional network structure. Examples of such polymers are polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-propylene-dicyclopentadiene terpolymers, polybutadiene, natural rubber, polyamide, polyvinyl alkyl ether, styrene-butadiene rubber. styrene copolymers such as styrene copolymers, vinyl chloride copolymers such as vinyl chloride/vinyl acetate copolymers, ethylene/vinyl acetate copolymers, polyesters or unsaturated polyesters, or mixtures of these polymers. The new copolymer can be used in unsaturated polyester materials.
In particular, they exhibit particularly good adhesive action when used together with copolymerizable solvents. In this case, the acid component of the polyester consists of unsaturated dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, and additional unsaturated dicarboxylic acids such as phthalic acid, isophthalic acid, adipic acid, etc. You can leave it on. Alcohol components include difunctional alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, neopentyl glycol, and the like. Suitable copolymerizable solvents include, for example, styrene, diallyl phthalate, acrylic acid.
tert.butyl ester. The polymerizable solvent is
It can reach up to 60% of polyester solution. Fillers, pigments or dyes with which the polymers can be bonded using the novel adhesives according to the invention include inorganic oxide materials such as silicon dioxide-containing materials, metals, alloys, metal oxides, etc. include. Examples of silicon dioxide-containing materials are glass, quartz, ceramics, sand, brick, asbestos and clay. The metal in such a combination is
Suitable are primarily aluminum, zinc, tin, magnesium, silver, nickel, and also metal alloys such as steel, chromium-nickel, bronze, or metals which have been subjected to a surface treatment, for example with phosphates. Examples of metal oxides include aluminum oxide, zinc oxide, titanium oxide,
Iron oxide and chromium oxide can be counted. The adhesive according to the invention can be used to produce a combination of a polymer and the above-mentioned inorganic oxide type material in a manner known per se, as described, for example, in German Pat. No. 1,270,716. It is done. Example 1 In a round bottom flask equipped with a reflux condenser, thermometer, stirrer, and gas line, 88.8 g of distilled vinyl acetate (VAC), 5 g of distilled vinyl chloroacetate (VCAC), and distilled vinyltrimethoxysilane ( 6.2 g (VTMO), 100 g of distilled acetic acid ethyl ester were weighed out and the flask contents were heated to 75° C. with stirring and a slow passage of nitrogen. Then, 0.1 g of azoisobutyric acid nitrile (AIBN) was added. After 2 and 5 hours, a further 0.1 g of AIBN was added. After a total reaction time of 7.5 hours, 500 ml of toluene were added and the acetate was distilled off within 2 hours. Then, the contents of the flask were 110
It was kept at ℃. For yield determination, 1/ of the weight of the solution
10 was removed and the solvent was evaporated under reduced pressure on a rotary evaporator. The conversion rate reached 97.5%. The reduced viscosity (ηred) of a 1% solution of the solid in acetate ester amounts to 0.37 (20° C., Ostwald viscometer). Elemental analysis is
It showed a silicon content of 1.18% and a chlorine content of 1.51%. 87.75g of polymer (equivalent to 0.0373 gram atom of chlorine)
The remainder of the solution containing was made up to 585 g with toluene,
Tetrabutylammonium bromide 0.9g, tert.−
Add 0.18 g of butylbrenz catechin and 3.86 g (0.041 mol) of solid powdered sodium acrylate,
Stir the mixture for 3 hours under nitrogen atmosphere.
It was kept at 110℃. The solids were filtered off. 100% of the calculated amount was obtained by quantification of salt by Holhardt, which corresponds to complete replacement of chlorine atoms by acryloxy groups. 100 g of the filtrate was diluted with 260 g of toluene and the resulting mixture was used as an undercoat solution. An acrylate double bond was confirmed at approximately 1640 cm ^-1 by infrared measurement of the sheet produced by the casting method. Five slides with a fat-free surface were mounted at a tilt angle of approximately 80° and moistened with a 5% primer solution.
After the coating had dried for 10 minutes, the primed board was post-treated for 1 hour at 110°C in a drying box, and the coated surface was coated with cobalt caprylate for 100 g of resin.
Styrol-containing, boil-resistant UP resin (Palatal) containing 2 g, 1 g acetylacetone peroxide
A 1 mm thick layer of A410, a commercially available product from BASF, was provided. After storage for 1 hour at 23° C. under a CO ₂ atmosphere, the painted glass slides were post-treated at 100° C. for 2 hours. As a comparative test, unprimed slides were applied with UP resin in the same manner. The bond between the resin layer and the glass was tested by immersion in boiling water. The UP resin peeled off after a few minutes on the unprimed glass slides, but remained good on the primed slides even after 3 hours of boiling. The bond between the glass and the UP resin remained good even after a 1 hour boiling time in water.

【table】

Table: Examples 2 to 10 Several copolymers were prepared in which one of the ethylenically unsaturated structural units was bonded to a halogencarboxylic acid group. To this end, a radical-initiated solution according to Example 1 was prepared using vinyltrimethoxysilane (VTMO), vinyl chloroacetate (VCAC) and vinyl acetate (VAC) as ethylenically unsaturated monomers in the weights listed in Table 1. The reaction was carried out using a polymerization method. The amount of azoisobutyric acid nitrile added in small quantities is <98% in less than 24 hours.
% polymerization reaction was achieved. Acetate ester was used as solvent, the weight ratio of solvent weight to monomer mixture weight varying in the individual examples from 4:1 to 1:4. The acetate ester was replaced in the described manner by an amount of toluene such that the weight proportion of the polymer in the triol solution was 15%. After addition of 0.2 g of hydroquinone monomethyl ether, 0.5% by weight of methyltricaprylammonium chloride, the structure of the polymer with a structural base unit having one acrylic group is changed to the above solution and acrylic for every gram atom of chlorine in the starting polymer. This is carried out by reaction with solid powdered sodium acrylate in an amount such that 1.1 mol of sodium acrylate is obtained. In that case, the reaction mixture is 90% of the stoichiometrically possible amount.
Keep at boiling temperature until more salt separates. After its filtration, the solids content of the resulting polymer solution was adjusted to 5% by the addition of toluene and the solution was tested using it as a primer as described in Example 1. Example 11 A copolymer having 3.3% by weight of vinyltriethoxysilane, 5.4% by weight of vinyl chloroacetate, 40.8% by weight of vinyl acetate and 50.5% by weight of N-vinylpyrrolidone as ethylenically unsaturated monomers was prepared in a solution according to example 1. Manufactured by polymerization method. Truol
A toluene solution containing 100 g of polymer in 567 g was reacted with 4.63 g of sodium acrylate at 110° C. for 3 hours in the presence of 1 g of tetrabutylammonium chloride and 0.2 g of hydroquinone monomethyl ether. After filtration, add toluene to half of this solution.
Added 167g and added 500g of water. The resulting emulsion was tested as a primer according to Example 1. The toluol was evaporated from another half of the toluol starting solution and the residue was taken up in 950 g of water. The resulting 5% solution was also used as a primer and tested. From the inspection, the bond between glass and UP resin is
After a boiling time of 1 hour in water, the results were still good in all cases. Example 12 As ethylenically unsaturated monomers, 10.3% by weight of vinyl-tris-(2-methoxy-ethoxy)-silane, 4.1% by weight of vinyl chloroacetate, vinyl acetate
A copolymer having 85.6% by weight was prepared by the method of solution polymerization according to Example 1. A toluol solution containing 100 g of polymer in 567 g of toluene was mixed with 1 g of tetrabutylammonium bromide and p-tert-
In the presence of 0.2 g of butylbrenzcatechin, it was reacted with 4.64 g of potassium methacrylate at 110° C. for 2 hours.
After filtration, the solution was diluted with 1333 g of toluene and Example 1
It was tested as a primer by. The bond between the glass and the UP resin remained good even after 2 hours of boiling time in water. Example 13 Methacryloxypropyltrimethoxysilane
A copolymer having 24.5% by weight of vinyl acetate, 5.5% by weight of vinyl acetate and 70.0% by weight of 2-ethylhexyl acrylate was mixed with 2% of benzoyl peroxide and 2% of dodecanethiol (relative to the total amount of monomers) in toluene solution. Produced by polymerization of monomers under use. A toluol solution containing 200 g of polymer in 1134 g of toluene was reacted with 9.44 g of sodium acrylate at 110 DEG C. for 3 hours in the presence of 2 g of N-laurylpyridinium bromide and 0.4 g of hydroquinone. After filtration, add 666g of toluol to this solution,
Tested as a primer using the method described in Example 1. The bond between the glass and the UP resin remained good even after a 3 hour boiling period in water. Example 14 5.1% by weight of vinyltrimethoxysilane and 90.8% by weight of vinyl acetate as ethylenically unsaturated monomers
A copolymer containing 4.1% by weight of vinyl chloroacetate was prepared by the method of solvent polymerization according to Example 1. A toluol solution containing 100 g of polymer in 567 g of toluene was mixed with 3.52 g of sodium acrylate in the presence of 1 g of tetrabutylammonium bromide and 0.2 g of hydroquinone monomethyl ether.
The reaction was carried out at 100°C for 2 hours. After filtration of the solids, the toluol was evaporated from the solution using a rotary evaporator. Dissolve 3 g of the evaporation residue in 4.5 g of styrene and mix the solution with 92.5 g of a commercially available UP resin mixture (Palatal A410).
Mixed with water. After addition of 2 g of cobalt octoate and 1 g of acetylacetone peroxide, the mixture was applied in such an amount that a 2 mm thick layer was formed on 5 glass slides. After storage for 1 hour at 23° C. under a CO ₂ atmosphere, the coated glass plates were post-treated at 100° C. for 2 hours. After boiling in water for 1 hour, the bond between the UP resin and the glass was still good. Example 15 A copolymer containing 7.0% by weight of vinyltriethoxysilane, 4.1% by weight of vinyl chloroacetate and 88.9% by weight of vinyl acetate as ethylenically unsaturated monomers was prepared by the method of solvent polymerization according to Example 1. A toluol solution containing 100 g of polymer in 567 g of toluene was mixed with 3.52 g of sodium acrylate, 1 g of tetrabutylammonium bromide and p-tert.
- Reacted with 3.52 g of sodium acrylate at 110° C. for 2 hours in the presence of 0.2 g of butylbrenz catechin. After filtration, the solution was diluted with 1333 g of toluene and tested as a primer according to Example 1. The bond between the glass and the UP resin remained good even after 2 hours of boiling time in water. Comparative Example 1 A copolymer having 95.8% by weight of vinyl acetate and 4.2% by weight of vinyltriethoxysilane was prepared according to Example 1. 50g of polymer in 950g of toluene
A solution containing was tested as a primer. When immersed in boiling water, the UP resin layer separated from the glass slide after a few minutes. Comparative example 2 Vinyl acetate 89.9% by weight, vinyl chloroacetate 10.1%
A copolymer having a weight percent of
and reacted at 110°C for 3 hours. After that, the precipitated salt was filtered off, and the resulting filtrate was mixed with toluol.
It was diluted with 666 g and used as a primer according to Example 1 and tested. When immersed in boiling water, the UP resin layer separated from the glass slide after a few minutes.

Claims (1)

[Claims] 1 Produced by radical polymerization and having a reduced viscosity of 0.02 to 2.0, with the general formula: [In the formula, Hal is a halogen atom which may be optionally substituted with an acrylic acid or methacrylic acid group, R is a hydrogen atom or a methyl group, and R ¹ is 1 to
Alkyl group with 16 C-atoms, R ² is 1-4
alkyl radicals having a C-atom of General formula ~ [Formula] [Formula] [Formula] [Formula] (In the formula, R represents the above, R ³ is a hydrogen atom or an alkyl group having 1 to 18 C-atoms, and R ⁴ is a hydrogen atom or represents an alkyl group having 1 to 4 C atoms), B is one of the non-functional production basic units of the general formula ~ [Formula] [Formula] [Formula] (where n is 3 to 5 and Frequently, the ring between the two C-atoms may be interrupted by an oxygen, R ⁵
is an alkyl group having 1 to 3 C-atoms and R
is a hydrogen atom or a methyl group) and a and b each represent 0 to 99% by weight and the sum of a and b = 0 to 99% ] copolymer. 2 with reduced viscosity from 0.02 to 2.0, general formula: [In the formula, Hal is a halogen atom which may be optionally substituted with an acrylic acid or methacrylic acid group, R is a hydrogen atom or a methyl group, and R ¹ is 1 to
Alkyl group with 16 C-atoms, R ² is 1-4
alkyl radicals having a C-atom of General formula ~ [Formula] [Formula] [Formula] [Formula] (In the formula, R represents the above, R ³ is a hydrogen atom or an alkyl group having 1 to 18 C-atoms, and R ⁴ is a hydrogen atom or represents an alkyl group having 1 to 4 C-atoms), B is one of the non-functional structural basic units of the general formula ~ [Formula] [Formula] [Formula] (where n is 3 to 5 and Frequently, the ring between the two C-atoms may be interrupted by an oxygen, R ⁵
is an alkyl group having 1 to 3 C-atoms and R
is a hydrogen atom or a methyl group) and a and b each represent 0 to 99% by weight and the sum of a and b = 0 to 99% ] A method for producing a copolymer by radical polymerization, which comprises reacting a copolymer in which one of the basic structural units has an α-halogen carboxylic acid group with an alkali salt of acrylic acid or methacrylic acid. Polymer manufacturing method. 3. The method of claim 2, wherein the reaction is carried out in solution in the presence of a phase change catalyst. 4. The method according to claim 2 or 3, wherein the reaction is carried out in the presence of an acrylic compound polymerization inhibitor. 5. The method according to any one of claims 2 to 4, wherein a quaternary ammonium salt or a phosphonium salt is used as a phase conversion catalyst. 6 Produced by radical polymerization, with reduced viscosity from 0.02 to 2.0, general formula: [In the formula, Hal is a halogen atom which may be optionally substituted with an acrylic acid or methacrylic acid group, R is a hydrogen atom or a methyl group, and R ¹ is 1 to
Alkyl group with 16 C-atoms, R ² is 1-4
alkyl radicals having a C-atom of General formula ~ [Formula] [Formula] [Formula] [Formula] (In the formula, R represents the above, R ³ is a hydrogen atom or an alkyl group having 1 to 18 C-atoms, and R ⁴ is a hydrogen atom or represents an alkyl group having 1 to 4 C-atoms), B is one of the non-functional structural basic units of the general formula ~ [Formula] [Formula] [Formula] (where n is 3 to 5 and Frequently, the ring between the two C-atoms may be interrupted by an oxygen, R ⁵
is an alkyl group having 1 to 3 C-atoms and R
is a hydrogen atom or a methyl group) and a and b each represent 0 to 99% by weight and the sum of a and b = 0 to 99% ] An adhesive between an inorganic oxide material and a polymer, characterized in that it contains a copolymer of: